Cellulose derivative compositions



UNITED STATES PATENT si n nuywuw 2,113,653 CELLULOSE DERIVATIVE GOMI'OSITIONS James Karr Hunt and George Henry Latham,

W ngton, DeL, assignors to E. I. do Pent deNcmours & Company, Wilmington, Dei, a corporation of Delaware No Drawing. Original application July 15., 1833,

Serial No. 680,656. Divided and this appiicaon April 24, 1936, Serial N0. 76,261

av Claims.

inhibiting agents for use in-celiulose derivative compositions. I However, the heretofore suggested compounds are usually either unsatisfactory as re M wards the inhibition of rancidity, orthey'seriously'afiect the'i'n'itial color of cellulose derivative clones, 'cause' discoloration of films deposited fromthe dopes on exposure to the sunlight, render such films sensitive to water, cause spotting to or fading of the color, or else have an objectionable odor. 'Most of the prior art has related onlybroadly to the inhibition of rancidity in oils and has'giv'en no indication of the suitability of suggested compoundsforuse in cellulose derive- 25 tivejd opes. The mere suggestion of a compound as a'rancidity inhibitor for oils is of practically.

' no value toward the selection of an agent having that unique combination of properties which will make it satisfactory for use in cellulose det0 rivative dopes; particularly white or light colored cellulose nitrate compositions. An object of the present invention is to provide improved cellulose derivative compositions forfcoating artificial leather, and the like, con- 35 taining a, non-drying or semi-drying fatty body and a rancidity inhibiting agent therefor. ther object is to provide such compositions containing a non-drying or semi-drying fatty body having a tendency to become rancid and having, I in the raw state, a normal iodine number below 1 85 and a rancidity inhibiting agent therefor 'which will not affect the initial color of the composition; causediscoloration of films deposited therefrom on exposure to the sunlight, render said'fllms sensitive to water, cause spotting or fading of the color, or have an objectionable odor-. Other objects of the invention will be apparent from the, description given hereinafter.

'The above objects are accomplished accordingto the, presentinvention by incorporating in a cellulose derivative coating composition containing anon-drying or semi-drying fatty body hav- 3 ing a tendency to become rancid and having, in the raw state, a normal iodine number below 135,

A fur-.

but preferably below 12 0, an agent enema from. the group consisting of my! basic acids.

Among the aryl boric acids found particulariy adapted for the purpose of the present invention are:

B(OH): 313(05):

w E, .i \l/ EH2 phony] boric acid p-tolyl hci'ie acid These compounds are comm Jigby the formula where R'ls any monovaient organic radical to the boron atom through an aromatic ct atom, and R1 is hydroityl or a monovaicnt radical joined to boron through an. aromatic car bon atom. Other suitable looric acids this general formula are alpha-naphthyl Ecoric acid, di-p-anisyl boric acid, di-beta naphthgl lactic acid, and p-carboxy=phenyl boric acid.

It has been found. that the above class of compounds has pmberties which are remarkably well adapted for using said compounds in cellulose derivative compositions containing non" drying and semi-drying oils and other fatty bodies tending to become rancid. That is, these compounds are efiective for inhibiting rancidity in compositions containing non-drying and semidrying fatty glycerides which have a tendency. to become rancid and have, in the raw state, normal iodine number below 135 and particularly in such oils having an iodine number below i225; do not give an objectionable odor to the compost tions, do not give rise to objectionable discoloration of the compositions, and do'not render the compositions sensitive-to water.

In order to test the efi'ect of our compounds in coating compositions or dupes employed in the manufacture of artificial leather a representative dope was prepared as follows:

Parts (by weight) Inhibitor (2% based on castor oil content) 0.36

mixed. The inhibitor was added as an alcoholic solution along with the pigment in oil.

In order to determine the eii'ect of the lamb-- itors on the color of a dope of this type, the pigment consisted of lithopone or a mixture of 98.5% lithopone and 1.5% ultramarine blue. The compositions containing these pigments, because of their white or pale blue color, are highly susceptible to discoloration by inhibitors of the, wrong type, and also lend themselves well to observations for water spotting".

By the term water spotting" is'meant a color change, suchas fadin which takes place when the artificial leather is brought into contact with water.

A suitable procedure for testing rancldity inhibitors in compositions of the above type follows: Various dopes are applied to pieces of-fabric in the usual manner for making artificial leather, which treated pieces of fabric are then subjected to the following tests. -A sample of treated fabric of standard size g., 2" x 5") is placed in a small glass-stoppered flask and stored at a temperature of about 65 C. The various bottles are opened daily, or at other suitable .intervals, and, from the odor emitted, a deter- 'mination as to when rancidity develops is made. The various pieces of treated fabric are subjected to exposure to the light from a glass-enclosed carbon are .for 16 hours and the change in color is compared with that of a sample of cloth treated with the same dope containing no inhibitor, in order to determine the efiect of the in'-' hibitors on the color change caused by exposure to sunlight.

A small strip of each sample of the treated fabric is immersed in water for 2 days and then dried. A comparison of the samples will disclose the effect of the inhibitors on water spotting or color change caused by the water.

The following table discloses the results obtained by the use of certain of our preferred in- 'hibitors when incorporated in an artificial leather prepared as above described. In each case, 2%

of the inhibitor, based on the castor oil, was

employed.

Table I ci d fi 01 I w t Inhibitor developchanges spotting ment' 7 None None None None 100+ None None ing or semi-drying oil, together with an inhibitor as above described.

, which may be treated satisfactorily bodies having a 'phe're. Glycerol esters are most employed. Howeveriitg these specific-amounts,

percent of the inhibitor,

as larger or smaller'proportions of the inhibitor may be used to advantage. inhibitor will depend upon the It is practically never The''- proportion of." particular type of, composition, and especially the. kind of oil usedi necessary to use-more tha'n 5% of inhibitor, based on the oil, and insome cases as little as 0.25% is 'useful. of inhibitor is given by weight and not'by volume.

The inhibitors have been disclosed specifically I The percent in coating compositions for dopes such-'a's are", generally used in the manufacture of artificialleather, said coating compositions containing castor oil.

to be employed in other types of cellulose deriva- However, the inhibitors are adapted tive, compositions containing non-drying and semi-drying fatty bodies which have.-a tendencyto become rancid and have, in the raw state a normal iodine number below 135,=or in such products when employed for other. purposes. For

example, the inhibitors of the present'invention may be employed'in cellulose derivative compo-1 sltions containing, 'resins and softeners derived from the various fatty acid glycerides.

Among the non-drying and semi-dryingolls" with the in-'- hibitors of the present invention, are olive. oil;*

rapeseed oil, codliver oil, corn oil, peanut oil,

cocoanut oil, cottonseed oil, palm QiL'neats-Toot oil, butter fat, lard, beef tallow, 'wooll fat, and the like.

various treatments, such as These oils,fats, and tallows may be. raw. or may have been previously subjectedto' blowing with air at}, elevated temperatures, simple'heat treatments,

and the like, or the oils maybe employed in making resins and softeners for the expression non-drying and semi-drying,

having, in the raw state, a normal iodine include bodies of a resinous, oily,

orwa'xy nature, having aniodine number below 135, which tendv use" in artificial I leather and'similar compositions. Accordingly,"

tendency to become rancid and number below as used in the claims, is intended to;

to become rancid with exposure to the atmosliable to ran-' 1" cidiflcationghence this invention is most concerned with such' esters.

However the present inhibitors can also be added with advantage to 2 other fatty acid esters, such as those of ethyl;' alcohol, butyl alcohol, mixtures of higher allphatic monohydric alcohols, ethoxyethyl. alcohol, ethylene glycol, propylene glycol, diethylene glycol, pentaerythritol, benzyl alcohol, et cetera.- Fatty glycerides to which the present inhibitors.

can-be added with especial advantageare those I U given in International Critical Tables volume II, pages 201-205, under General Index Numbers 0.5- v

51 and 95-149 inclusive. The terminology used in the claims, referred to above 'is intended to include all the above-monohydric or polyhydric alcohol esters. v This is a division of our copending application I Serial No. 680,656, filed July 15, 1933.

While certain compounds or general classes and certain fatty bodies employed in particular compositions have been disclosed, it is to" be understood that other compounds of thesame class may be employed for treating other fatty'bodles I of the. type described, and the proportions and l the constituents of the compositions in which; they are employed may be widely varied without departing from the spirit of the invention. Ac-- cordingly, the scope of the lnventionris tobe .18

1. A composition comprising a cellulose deinhibitor therefor, an aryl boric acid in a small percent based on the fatty substance.

3. A composition comprising a fatty substance of the group consisting of non-drying and semidrying fatty glycerides having a tendency to become rancid and having, in the 'raw state, a normal iodine number below 135 and, as a rancidity 5. A composition comprising a fatty substance of the group consisting of non-drying and semidrying fatty glycerides having a tendency to become rancid and having, in the raw state, a normal iodine number below and, as a rancidity inhibitor therefor, a tolyl boricvacid in a small percent based on the fatty glyceride.

6. A composition comprising a fatty substance of the group consisting of non-drying and semidrying fatty glycerides having a tendency to become rancid and having, in the raw state, a normal iodine number below 135 and, as a rancidity inhibitor therefor, p-tolyl boric acid in a small percent based on the fatty glyceride.

7.'A composition comprising a fatty substance of the group consisting of non-drying and semidrying fatty glycerides having a tendency to become rancid and having, in the raw state, a normal iodine number below 135 and, as a rancidity inhibitor therefor, a naphthyl boric acid in a small percent based on the fatty glyceride.

8. A compositioncomprising a. fatty substance of the group consisting of non-drying and semidrying fatty glycerides having a tendency to become rancid and having, in the raw state, a normal iodine number below 135 and, as a rancidity inhibitor therefor, alpha-naphthyl boric acid in a small percent based on the fatty glyceride.

JAMES KARR HUNT. GEORGE HENRY LATHAM. 

